Results of a comprehensive study on the chemical structure of lignin from plantation Eucalyptus globulus Labill are presented. Lignin has been isolated by a modified mild acidolysis method and thoroughly characterized by functional group analysis, by a series of degradation techniques (nitrobenzene oxidation, permanganate oxidation, thioacidolysis, and Py-GC-MS), and (1)H and (13)C NMR spectroscopy. Plantation Eucalyptus globulus lignin was found to be of the S/G type with an extremely high proportion of syringyl (S) units (82-86%) and a minor proportion of p-hydrophenyl propane (H) units (roughly 2-3 mol %). Unknown C-6 substituted and 4-O-5' type syringyl substructures represent about 65% of lignin "condensed" structures. Eucalypt lignin showed high abundance of beta-O-4 (0.56/C(6)) structures and units linked by alpha-O-4 bonds (0.23/C(6)). The proportion of phenylcoumaran structures was relatively low (0.03/C(6)). Different kinds of beta-beta substructures (pino-/syringaresinol and isotaxiresinol types) in a total amount of 0.13/C(6) were detected. ESI-MS analysis revealed a wide molecular weight distribution of lignin with the center of gravity of mass distribution around 2500 u.
Industrial hardwoods such as Eucalyptus species, Betula pendula, and Acacia mangium required different chemical charges during kraft pulping and presented distinct profiles of polysaccharides removal. The corresponding kraft pulps showed different chlorine dioxide consumption during bleaching. Woods and corresponding kraft pulps were characterized by chemical methods, 1 H and 13 C NMR spectroscopy, X-ray diffraction analysis, and gel permeation chromatography. The ease of lignin degradation and dissolution was essentially determined by differences in the proportion of syringyl and guaiacyl units and in the degree of condensation. The bleaching response was shown to be related also to the content of β-O-4 structures in the residual lignin. The relative stability of xylans during the pulping was suggested to be associated with differences in structure and molecular weight. The higher retention of Eucalyptus xylans was attributed essentially to their peculiar structure, including O-2-substituted uronic acid groups linked to other cell wall polysaccharides.
High-performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-ESI-MS) and tandem mass spectrometry (MS(n)) were used to investigate the phenolic constituents in methanol, water, and methanol/water extracts of Eucalyptus globulus Labill. bark. Twenty-nine phenolic compounds were identified, 16 of them referenced for the first time as constituents of E. globulus bark, namely, quinic, dihydroxyphenylacetic, and caffeic acids, bis(hexahydroxydiphenoyl (HHDP))-glucose, galloyl-bis(HHDP)-glucose, galloyl-HHDP-glucose, isorhamentin-hexoside, quercetin-hexoside, methylellagic acid (EA)-pentose conjugate, myricetin-rhamnoside, isorhamnetin-rhamnoside, mearnsetin, phloridzin, mearnsetin-hexoside, luteolin, and a proanthocyanidin B-type dimer. Digalloylglucose was identified as the major compound in the methanol and methanol/water extracts, followed by isorhamnetin-rhamnoside in the methanol extract and by catechin in the methanol/water extract, whereas in the water extract catechin and galloyl- HHDP-glucose were identified as the predominant components. The methanol/water extract was shown be the most efficient to isolate phenolic compounds identified in E. globulus bark.
The monomeric composition of suberin extracts obtained by gradual alkaline methanolysis of Quercus suber cork was determined by gas chromatography-mass spectrometry (GC-MS). Results show that 1-alkanols and alkanoic and alpha,omega-alkanedioic acids are preferentially removed upon mild alkaline conditions, whereas mid-chain-modified omega-hydroxyalkanoic acids are preferentially removed under stronger alkaline conditions. Saturated omega-hydroxyalkanoic acids are found to be abundant in all suberin extracts. These results are consistent with two distinct suberin fractions with different locations in cork cell walls and/or esterification degrees. It is proposed that these fractions correlate with the two main suberin peaks in the solid state (13)C NMR spectra of cork and suberin extracts. Quantitative GC-MS analysis showed that suberin monomers comprise approximately 30% (w/w) of the suberin extracts, the remaining comprising nonvolatile structures with high M(n) values, as measured by vapor pressure osmometry. The presence of a large fraction of high molecular weight aliphatic structures in suberin extracts is supported by the corresponding NMR spectra.
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